US10160819B2 - Ethylene/alpha-olefin/polyene based compositions - Google Patents

Ethylene/alpha-olefin/polyene based compositions Download PDF

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US10160819B2
US10160819B2 US14/434,208 US201314434208A US10160819B2 US 10160819 B2 US10160819 B2 US 10160819B2 US 201314434208 A US201314434208 A US 201314434208A US 10160819 B2 US10160819 B2 US 10160819B2
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Colin LiPiShan
Timothy E. Clayfield
Sonja M. Delatte
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/64003—Titanium, zirconium, hafnium or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/64168—Tetra- or multi-dentate ligand
    • C08F4/64186—Dianionic ligand
    • C08F4/64193—OOOO
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/17—Viscosity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/19—Shear ratio or shear ratio index
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/21—Rubbery or elastomeric properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/25—Cycloolefine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article

Definitions

  • WO 2007/136494 disclosed ethylene/alpha-olefin/diene polymers prepared from a catalyst composition comprising a zirconium complex of a polyvalent aryloxyether.
  • WO 2006/009976 discloses processes for preparing polyolefins in the presence of a perfluorocarbon or hydrofluorocarbon with an activated, nonmetallocene, metal-centered, heteroaryl ligand catalyst.
  • Rubber compositions are also disclosed in the following: WO2011/008837, WO2012/092491, US20060183631, WO2011/163176, EP1433812A1, WO2011/041230, WO2006/009976, WO2000/26268, U.S. Pat. No. 8,178,031, EP751182A1, EP718324A1, WO2011/0065877, JP04132672B2 (abstract), JP2004035813 (abstract), EP1433812A1.
  • the invention provides a composition comprising a first composition that comprises at least one ethylene/alpha-olefin/nonconjugated polyene interpolymer;
  • FIG. 1 depicts a plot of “13C NMR % Peak Area” versus “weight percent C2 (13C NMR)” for several inventive (first composition) and comparative compositions.
  • the invention provides a composition comprising a first composition that comprises at least one ethylene/alpha-olefin/nonconjugated polyene interpolymer;
  • the first composition has a Mooney Viscosity (ML1+4, 125° C.) greater than, equal to 10, and
  • the first composition has a “13C NMR % Peak Area,” which is the ⁇ [(13C NMR peak area from 21.3 ppm to 21.8 ppm) divided by the (total integral area from 19.5 ppm to 22.0 ppm)] ⁇ 100 ⁇ , that is greater than 3.5 percent, as determined by 13C NMR.
  • the inventive composition may comprise a combination of two or more embodiments described herein.
  • the first composition may comprise a combination of two or more embodiments described herein.
  • the ethylene/alpha-olefin/nonconjugated polyene interpolymer may comprise a combination of two or more embodiments described herein.
  • the first composition has a “13C NMR % Peak Area,” which is the ⁇ [(13C NMR peak area from 21.3 ppm to 21.8 ppm) divided by the (total integral area from 19.5 ppm to 22.0 ppm)] ⁇ 100 ⁇ , that is greater than, or equal to, 4.0 percent, further greater than, or equal 5.0 percent, as determined by 13C NMR.
  • the first composition has a “13C NMR % Peak Area,” which is the ⁇ [(13C NMR peak area from 21.3 ppm to 21.8 ppm) divided by the (total integral area from 19.5 ppm to 22.0 ppm)] ⁇ 100 ⁇ , that is greater than, or equal to, 6.0 percent, further greater than, or equal 7.0 percent, as determined by 13C NMR.
  • the first composition has a “13C NMR % Peak Area,” which is the ⁇ [(13C NMR peak area from 21.3 ppm to 21.8 ppm) divided by the (total integral area from 19.5 ppm to 22.0 ppm)] ⁇ 100 ⁇ , that is greater than, or equal to, 8.0 percent, further greater than, or equal 9.0 percent, further greater than, or equal 10.0 percent, as determined by 13C NMR.
  • the first composition has a “13C NMR % Peak Area,” which is the ⁇ [(13C NMR peak area from 21.3 ppm to 21.8 ppm) divided by the (total integral area from 19.5 ppm to 22.0 ppm)] ⁇ 100 ⁇ , that is greater than, or equal to, 12.0 percent, further greater than, or equal 14.0 percent, further greater than, or equal 16.0 percent, as determined by 13C NMR.
  • the first composition comprises greater than, or equal to, 90 weight percent, further greater than, or equal to, 95 weight percent, further greater than, or equal to, 98 weight percent, of the ethylene/alpha-olefin/nonconjugated polyene interpolymer, based on the weight of the first composition.
  • the first composition comprises greater than, or equal to, 30 weight percent, further greater than, or equal to, 40 weight percent, further greater than, or equal to, 50 weight percent, of the ethylene/alpha-olefin/nonconjugated polyene interpolymer, based on the weight of the first composition.
  • the first composition further comprises a second ethylene/alpha-olefin/nonconjugated polyene interpolymer.
  • the first composition comprises greater than, or equal to, 90 weight percent, further greater than, or equal to, 95 weight percent, further greater than, or equal to, 98 weight percent, of the sum weight of the second ethylene/alpha-olefin/nonconjugated polyene interpolymer and the ethylene/alpha-olefin/nonconjugated polyene interpolymer, based on the weight of the first composition.
  • the first composition further comprises a second ethylene/alpha-olefin/nonconjugated polyene interpolymer.
  • the first composition comprises greater than, or equal to, 30 weight percent, further greater than, or equal to, 40 weight percent, further greater than, or equal to, 50 weight percent, of the sum weight of the second ethylene/alpha-olefin/nonconjugated polyene interpolymer and the ethylene/alpha-olefin/nonconjugated polyene interpolymer, based on the weight of the first composition.
  • the first composition meets the following relationship: 13C NMR % Peak Area ⁇ 0.40(C2)+33%; wherein the “13C NMR % Peak Area,” is the ⁇ [(13C NMR peak area from 21.3 ppm to 21.8 ppm) divided by the (total integral area from 19.5 ppm to 22.0 ppm)] ⁇ 100 ⁇ , as determined by 13C NMR; and the “C2” is the weight percent of polymerized ethylene in the first composition, based on the weight of the first composition.
  • the first composition comprises from 40 to 80 weight percent ethylene, further from 45 to 75 weight percent ethylene, based on the weight of first composition.
  • the first composition comprises from 0.5 to 15 weight percent, further from 0.5 to 12 weight percent, further from 0.5 to 10 weight percent, further from 0.5 to 8 weight percent, further from 0.5 to 6 weight percent of the polyene, based on the weight of first composition.
  • the polyene is a diene, and further ENB.
  • the first composition has a viscosity at 0.1 rad/sec, 190° C., greater than, or equal to, 40,000 Pa ⁇ s, further greater than, or equal to, 45,000 Pa ⁇ s, further greater than, or equal to, 50,000 Pa ⁇ s.
  • the first composition has a Mooney Viscosity greater than, or equal to, 15, further greater than, or equal to, 20 (ML 1+4, 125° C.).
  • the first composition has a Mooney Viscosity greater than, or equal to, 30, further greater than, or equal to, 40 (ML 1+4, 125° C.).
  • the first composition has a Mooney Viscosity greater than, or equal to, 50, further greater than, or equal to, 60, further greater than, or equal to, 70 (ML 1+4, 125° C.).
  • the first composition has a Mooney Viscosity from 15 to 100, further from 20 to 80 (ML 1+4, 125° C.).
  • the first composition has a MWD less than, or equal to, 4.0, further less than, or equal to, 3.5, further less than, or equal to, 3.0.
  • the first composition has a MWD greater than, or equal to, 2.0, further greater than, or equal to, 2.1.
  • the first composition has a rheology ratio (V0.1/V100 at 190° C.) greater than, or equal to, 20, further greater than, or equal to, 23, and further greater than, or equal to, 25.
  • the first composition has a rheology ratio (V0.1/V100 at 190° C.) from 20 to 50, further from 22 to 45, further from 25 to 40.
  • the first composition has a viscosity at 0.1 rad/sec, 190° C., from 30,000 to 130,000 Pa ⁇ s, further from 35,000 to 125,000 Pa ⁇ s, further from 40,000 to 120,000 Pa ⁇ s.
  • the first composition has a weight average molecular weight (Mw) less than, or equal to, 350,000 g/mole, further less than, or equal to, 300,000 g/mole, further less than, or equal to, 250,000 g/mole.
  • Mw weight average molecular weight
  • the first composition has a weight average molecular weight (Mw) from 50,000 to 350,000 g/mole, further from 60,000 to 300,000 g/mole, further from 70,000 to 250,000 g/mole.
  • Mw weight average molecular weight
  • the first composition has a tan delta (0.1 rad/sec, 190° C.) from 0.70 to 1.90, further from 0.75 to 1.80, further from 0.77 to 1.70.
  • the first composition has a tan delta (0.1 rad/sec, 190° C.) from 1.00 to 1.90, further from 1.10 to 1.80.
  • the first composition comprises from 40 to 90 weight percent ethylene, further from 50 to 90 weight percent ethylene, further from 55 to 85 weight percent ethylene, and further from 60 to 80 weight percent ethylene, based on the weight of the first composition.
  • the first composition is present in an amount greater than, or equal to, 20 weight percent, further greater than, or equal to, 30 weight percent, and further greater than, or equal to, 40 weight percent, based on the weight of the composition.
  • the first composition may comprise a combination of two or more embodiments described herein.
  • the ethylene/alpha-olefin/nonconjugated polyene interpolymer may comprise a combination of two or more embodiments described herein.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer is an ethylene/ ⁇ -olefin/diene interpolymer (EAODM).
  • the interpolymer is an ethylene/propylene/diene terpolymer (EPDM).
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/alpha-olefin/nonconjugated polyene interpolymer has a rheology ratio (V0.1/V100 at 190° C.) greater than, or equal to, 20, further greater than, or equal to, 30, further greater than, or equal to, 40, further greater than, or equal to, 50.
  • the interpolymer is an EAODM, and further an ethylene/propylene/diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/alpha-olefin/nonconjugated polyene interpolymer has a rheology ratio (V0.1/V100 at 190° C.) from 20 to 80, further from 30 to 70, further from 40 to 60.
  • the interpolymer is an EAODM, and further an ethylene/propylene/diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the rheology ratio (V0.1/V100 at 190° C.) of the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer is that of the neat polymer (no oil, no filler).
  • the polymer may be stabilized with “ppm amounts” of one or more antioxidants and/or other stabilizers.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene has a viscosity at 0.1 rad/sec, 190° C., from 120,000 to 200,000 Pa ⁇ s, further from 130,000 to 190,000 Pa ⁇ s. further from 140,000 to 180,000 Pa ⁇ s.
  • the interpolymer is an EAODM, and further an ethylene/propylene/diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer comprises from 3.0 to 12.0 weight percent polyene, further from 4.0 to 10.0 weight percent polyene, and further from 5.0 to 7.0 weight percent polyene, based on the weight of the interpolymer.
  • the polyene is a diene.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer has a Mooney Viscosity greater than, or equal to, 30, further greater than, or equal to, 35, further greater than, or equal to, 40 (ML 1+4, 125° C.). Mooney viscosity is that of the neat polymer (no oil, no filler).
  • the polymer may be stabilized with “ppm amounts” of one or more antioxidants and/or other stabilizers.
  • the interpolymer is an EAODM, and further an ethylene/propylene/diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer has a MWD less than, or equal to, 3.5, further less than, or equal to 3.0, further less than, or equal to 2.5.
  • the interpolymer is an EAODM, further an ethylene/propylene/diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer has a MWD greater than, or equal to, 1.2, further greater than, or equal to 1.5, further greater than, or equal to 1.8.
  • the interpolymer is an EAODM, further an ethylene/propylene/diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer has a MWD greater than, or equal to, 1.7, further greater than, or equal to 2.0, further greater than, or equal to 2.2.
  • the interpolymer is an EAODM, further an ethylene/propylene/diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer has a weight average molecular weight (Mw) less than, or equal to, 400,000 g/mole, further less than, or equal to, 300,000 g/mole, further less than, or equal to, 200,000 g/mole.
  • the interpolymer is an EAODM, and further an ethylene/propylene/diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer has a weight average molecular weight (Mw) from 80,000 to 300,000 g/mole, further from 100,000 to 200,000 g/mole.
  • the interpolymer is an EAODM, and further an ethylene/propylene/diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer comprises from 40 to 90 weight percent ethylene, further from 50 to 90 weight percent ethylene, further from 55 to 85 weight percent ethylene, and further from 60 to 80 weight percent ethylene, based on the weight of the interpolymer.
  • the interpolymer is an EAODM, and further an ethylene/propylene/diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer is present in an amount greater than, or equal to, 20 weight percent, further greater than, or equal to 30 weight percent, and further greater than, or equal to 40 weight percent, based on the weight of the composition.
  • the interpolymer is an EAODM, further an ethylene/propylene/diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer, further an EAODM, and further an EPDM may comprise a combination of two or more embodiments as described herein.
  • the composition further comprises a crosslinking agent.
  • the composition further comprises an oil.
  • an inventive composition further comprises a filler.
  • Suitable fillers include, but are not limited to, clay, CaCO3, talc, carbon black, and mineral fibers.
  • the filler is present in an amount from 5 to 30 weight percent, based on the weight of the composition.
  • an inventive composition further comprises at least one stabilizer.
  • Suitable stabilizers include, but are not limited to, AO and UV stabilizers.
  • the inventive composition may comprise a combination of two or more embodiments described herein.
  • the invention also provides a crosslinked composition formed from an inventive composition of one or more embodiments described herein.
  • the invention also provides an article comprising at least one component formed from an inventive composition of one or more embodiments described herein.
  • the article is selected from the group consisting of profiles, injection molded parts, gaskets, automotive parts, building and construction materials, shoe components, and tubes.
  • the article is an automotive part.
  • the invention also provides an article comprising at least one component formed from a crosslinked composition of one or more embodiments described herein.
  • the article is selected from the group consisting of profiles, injection molded parts, gaskets, automotive parts, building and construction materials, shoe components, and tubes.
  • the inventive composition may comprise a combination of two or more embodiments described herein.
  • An inventive article may comprise a combination of two or more embodiments described herein.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymers (including the second ethylene/ ⁇ -olefin/nonconjugated polyene interpolymers), for the inventive compositions described herein, comprise, in polymerize form, ethylene, an ⁇ -olefin, and a nonconjugated polyene.
  • Suitable examples of ⁇ -olefins include the C3-C20 ⁇ -olefins, further C3-C10 ⁇ -olefins, and preferably propylene.
  • Suitable examples of nonconjugated polyenes include the C4-C40 nonconjugated dienes.
  • the ⁇ -olefin may be either an aliphatic or an aromatic compound.
  • the ⁇ -olefin is preferably a C3-C20 aliphatic compound, preferably a C3-C16 aliphatic compound, and more preferably a C3-C10 aliphatic compound.
  • Preferred C3-C10 aliphatic ⁇ -olefins are selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and more preferably propylene.
  • the interpolymer is an ethylene/propylene/-diene (EPDM) terpolymer.
  • the diene is 5-ethylidene-2-norbornene (ENB).
  • Illustrative nonconjugated polyenes include straight chain acyclic dienes, such as 1,4-hexadiene and 1,5-heptadiene; branched chain acyclic dienes, such as 5-methyl-1,4-hexadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, 5,7-dimethyl-1,7-octadiene, 1,9-decadiene, and mixed isomers of dihydromyrcene; single ring alicyclic dienes such as 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene; multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene, methyl
  • the polyene is preferably a nonconjugated diene selected from the group consisting of ENB, dicyclopentadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, and preferably, ENB, dicyclopentadiene and 1,4-hexadiene, more preferably ENB and dicyclopentadiene, and even more preferably ENB.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer comprises a majority amount of polymerized ethylene, based on the weight of the interpolymer.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer is an ethylene/ ⁇ -olefin/dene interpolymer.
  • the interpolymer is an EPDM.
  • the diene is ENB.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer has a molecular weight distribution (Mw/Mn) from 1.7 to 5.0, further from 1.8 to 4.0, further from 2.0 to 3.5, further from 2.0 to 3.0.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer is an ethylene/ ⁇ -olefin/dene interpolymer (EAODM).
  • the interpolymer is an EPDM.
  • the diene is ENB.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer has a Mooney viscosity, ML(1+4) at 125° C., greater than, or equal to, 20, further greater than, or equal to, 30, further greater than, or equal to 35.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer is an ethylene/ ⁇ -olefin/dene interpolymer.
  • the interpolymer is an EPDM.
  • the diene is ENB.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer has a Mooney viscosity, ML(1+4) at 125° C., less than 100, or less than, or equal to, 80, or less than, or equal to, 60.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer is an ethylene/ ⁇ -olefin/dene interpolymer.
  • the interpolymer is an EPDM.
  • the diene is ENB.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer has a Mooney viscosity, ML(1+4) at 125° C., from 20 to 100, or from 30 to 80, or from 35 to 60.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer is an ethylene/ ⁇ -olefin/dene interpolymer.
  • the interpolymer is an EPDM.
  • the diene is ENB.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer has a Mooney viscosity, ML(1+4) at 125° C., from 10 to 100, or from 15 to 90, or from 20 to 85.
  • the ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer is an ethylene/ ⁇ -olefin/diene interpolymer.
  • the interpolymer is an EPDM.
  • the diene is ENB.
  • Mooney viscosity is that of the neat interpolymer (or calculated viscosity of neat polymer for polymers that contain a filler, such as carbon black, and/or an oil).
  • the neat polymer refers to the polymer without filler and without oil.
  • An ethylene/alpha-olefin/nonconjugated polyene interpolymer may comprise a combination of two or more embodiments as described herein.
  • An ethylene/alpha-olefin/diene interpolymer may comprise a combination of two or more embodiments as described herein.
  • An EPDM terpolymer may comprise a combination of two or more embodiments as described herein.
  • Vulcanizing agents include, but are not limited to, sulfur-containing compounds, such as elemental sulfur, 4,4′-dithiodimorpholine, thiuram di- and polysulfides, alkylphenol disulfides, and 2-morpholino-dithiobenzothiazole; peroxides, such as di-tertbutyl peroxide, tertbutylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-(tertbutylperoxy) hexane, di-(tertbutylperoxyisopropyl) benzene, tertbutyl peroxybenzoate and 1,1-di-(tertbutylperoxy)-3,3,5-trimethylcyclohexane; metal oxides, such as zinc, magnesium, and lead oxides; dinitroso compounds, such as p-quinone-dioxime and p,p′-dibenzoylquinon
  • Sulfur can be a crystalline elemental sulfur or an amorphous elemental sulfur, and either type can be in pure form or supported on an inert carrier.
  • An example of a supported sulfur is Rhenogran S-80 (80% S and 20% inert carrier) from Rhein Chemie.
  • the sulfur containing compounds and the peroxides are the preferred vulcanizing agents, and the sulfur containing compounds are most preferred. It is understood that mixtures of these vulcanizing agents can be employed, though this is generally not preferred.
  • the amount of the vulcanizing agent can range from about 1 to 10 parts by weight, based upon 100 parts of the polymers in the composition.
  • Vulcanization temperatures and time employed are typical. Temperatures ranging from about 250° F. to about 440° F., and times ranging from about one minute to about 120 minutes can be employed.
  • Additional crosslinking agents include, but are not limited to, phenolic resins, azides, aldehyde-amine reaction products, vinyl silanes, hydrosilylation, substituted ureas, substituted guanidines; substituted xanthates; substituted dithiocarbamates; and combinations thereof. See Encyclopedia of Chemical Technology, Vol. 17, 2nd edition, Interscience Publishers, 1968; also Organic Peroxides, Daniel Seem, Vol. 1, Wiley-Interscience, 1970), which are incorporated by reference herein in their entirety.
  • the crosslinking agent may be a phenolic curing agent or a peroxide curing agent, with an optional co-agent, or hydrosilylation cross-linking agent with a hydrosilylation catalyst, or dibutyl tin dilaurate (“DBTDL”), with an optional co-agent alumina trihydrate (“ATH”), for silane-grafted interpolymer.
  • DBTDL dibutyl tin dilaurate
  • ATH co-agent alumina trihydrate
  • a phenolic resin and SnC12 is used for EPDM curing (peroxide, or sulfur or hydrosilation curing systems can also be used).
  • Suitable peroxides include, but are not limited to, aromatic dactyl peroxides; aliphatic dactyl peroxides; dibasic acid peroxides; ketene peroxides; alkyl peroxyesters; alkyl hydroperoxides (for example, diacetylperoxide; dibenzoylperoxide; bis-2,4-dichlorobenzoyl peroxide; di-tert-butyl peroxide; dicumylperoxode; tert-butyl-perbenzoate; tert-butylcumylperoxide; 2,5-bis (t-butylperoxy)-2,5-dimethylhexane; 2,5-bis (t-butylperoxy)-2,5-dimethylhexyne-3; 4,4,4′,4′-tetra-(t-butylperoxy)-2,2-dicyclohexylpropane; 1,4-bis-(t
  • the vulcanizing elastomer may be grafted to a vinyl silane monomer in the presence of a low level of peroxide via a separate reactive extrusion process.
  • Suitable vinyl silanes include, but are not limited to, vinyl trimethoxysilane, vinyl triethoxysilane.
  • the grafted elastomer may then be reacted with water to cure the polymer in the presence of a catalyst such as dibutyl tin dilaurate during the dynamic vulcanization process.
  • Suitable water sources include, but are not limited to, steam, water/ethylene glycol mixtures, aluminum trihydrate, and magnesium hydroxide. Either ethylene-alpha-olefin copolymers or ethylene-alpha-olefin-polyene terpolymers are suitable vulcanizing elastomers for this cure system.
  • Silicon hydride having at least two SiH groups in the molecule may be reacted with the carbon-carbon multiple bonds of the unsaturated rubber component in the presence of a hydrosilylation catalyst to form useful crosslinks during dynamic vulcanization.
  • Suitable silicon hydride compounds include, but are not limited to, methylhydrogen polysiloxanes, methylhydrogen dimethyl-siloxane copolymers, methylhydrogen alkyl methyl polysiloxanes, bis(dimethylsilyl)alkanes and bis(dimethylsilyl)benzene.
  • the amount of silicon hydride compound useful in the process of the composition can range from about 0.1 to about 10.0 mole equivalents of SiH per carbon-carbon double bond in the rubber, and preferably is in the range of about 0.5 to about 5.0 mole equivalents of SiH per carbon-carbon double bond in the rubber component of the thermoplastic elastomer.
  • Suitable catalysts for the hydrosilylation vulcanization reaction include transition metals of Group VIII such as palladium, rhodium, platinum and the like, including complexes of these metals.
  • the use of hydrosilylation crosslinking to dynamically vulcanize EPDM to produce TPV's was disclosed in U.S. Pat. No. 6,251,998 (Medsker, et al., Jun. 26, 2001), which is incorporated by reference herein in its entirety.
  • a crosslinking agent may comprise a combination of two or more embodiments as described herein.
  • Oils include, but are not limited to, petroleum oils, such as aromatic and naphthenic oils; polyalkylbenzene oils; organic acid monoesters, such as alkyl and alkoxyalkyl oleates and stearates; organic acid diesters, such as dialkyl, dialkoxyalkyl, and alkyl aryl phthalates, terephthalates, sebacates, adipates, and glutarates; glycol diesters, such as tri-, tetra-, and polyethylene glycol dialkanoates; trialkyl trimellitates; trialkyl, trialkoxyalkyl, alkyl diaryl, and triaryl phosphates; chlorinated paraffin oils; coumarone-indene resins; pine tars; vegetable oils, such as castor, tall, rapeseed, and soybean oils and esters and epoxidized derivatives thereof; and the like.
  • petroleum oils such as aromatic and naphthenic oils
  • the oil is present in an amount from 5 to 70 weight percent, further from 5 to 60 weight percent, further from 5 to 50 weight percent, based on the weight of the composition.
  • the oil is selected from the group consisting of nonaromatic oils, paraffinic oils, naphthenic oils, and combinations thereof.
  • Suitable oils include, but are not limited to, SUNPAR 2280, PARALUX 6001, HYDROBRITE 550, and CALSOL 5550.
  • An oil may comprise a combination of two or more embodiments as described herein.
  • An inventive composition may comprise one or more additional additives.
  • Suitable additives include, but are not limited to, fillers, antioxidants and antiozonants, UV stabilizers, flame retardants, colorants or pigments, and combinations thereof.
  • Fillers include, but are not limited to, carbon black, silicates of aluminum, magnesium, calcium, sodium, potassium and mixtures thereof; carbonates of calcium, magnesium and mixtures thereof; oxides of silicon, calcium, zinc, iron, titanium, and aluminum; sulfates of calcium, barium, and lead; alumina trihydrate; magnesium hydroxide; natural fibers, synthetic fibers, and the like.
  • antioxidants and antiozonants include, but are not limited to, hindered phenols, bisphenols, and thiobisphenols; and substituted hydroquinones.
  • Foaming agents such as azodicarbonamide, can be used for making a foam structure.
  • an inventive composition further comprises a thermoplastic polymer.
  • Polymers include, but not limited to, propylene-based polymers, ethylene-base polymers, and olefin multi-block interpolymers.
  • Suitable ethylene-base polymers include, but are not limited to, high density polyethylene (HDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE), homogeneously branched linear ethylene polymers, and homogeneously branched substantially linear ethylene polymers (that is homogeneously branched long chain branched ethylene polymers).
  • compositions of the present invention may be used to prepare a variety of articles or manufacture, or their component parts or portions.
  • inventive compositions may be converted into a finished article of manufacture by any one of a number of conventional processes and apparatus.
  • Illustrative processes include, but are not limited to, extrusion, calendering, compression molding, and other typical thermoset material forming processes.
  • Articles include, but are not limited to, sheets, foams, molded goods, and extruded parts. Additional articles include automotive parts, weather strips, belts, hoses, building profiles, wire and cable jacketing, flooring materials, gaskets, tires and tire components, computer parts, building materials and footwear components. A skilled artisan can readily augment this list without undue experimentation.
  • composition includes the material(s), which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition. Any reaction product or decomposition product is typically present in trace or residual amounts.
  • polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure) and the term interpolymer as defined hereinafter. Trace amounts of impurities, such as catalyst residues, can be incorporated within the polymer.
  • interpolymer refers to polymers prepared by the polymerization of at least two different types of monomers.
  • the term interpolymer thus includes the term copolymer (employed to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.
  • ethylene-based polymer refers to a polymer that comprises, in polymerized form, a majority weight percent of ethylene (based on the weight of the polymer), and optionally may comprise one or more comonomers.
  • ethylene-based interpolymer refers to a polymer that comprises, in polymerized form, a majority weight percent of ethylene (based on the weight of the interpolymer), and at least one comonomer.
  • ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer refers to a polymer that comprises, in polymerized form, ethylene, an ⁇ -olefin, and a nonconjugated polyene.
  • the “ethylene/ ⁇ -olefin/nonconjugated polyene interpolymer” comprises a majority weight percent of ethylene (based on the weight of the interpolymer).
  • ethylene/ ⁇ -olefin/diene interpolymer refers to a polymer that comprises, in polymerized form, ethylene, an ⁇ -olefin, and a diene.
  • the “ethylene/ ⁇ -olefin/diene interpolymer” comprises a majority weight percent of ethylene (based on the weight of the interpolymer).
  • ethylene/ ⁇ -olefin copolymer refers to a copolymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the copolymer), and an ⁇ -olefin, as the only two monomer types.
  • propylene-based polymer refers to a polymer that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the polymer), and optionally may comprise one or more comonomers.
  • propylene/ ⁇ -olefin copolymer refers to a copolymer that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the copolymer), and an ⁇ -olefin, as the only two monomer types.
  • propylene/ethylene copolymer refers to a copolymer that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the copolymer), and ethylene, as the only two monomer types.
  • compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.
  • the term, “consisting essentially of ” excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability.
  • the term “consisting of ” excludes any component, step or procedure not specifically delineated or listed.
  • the chromatographic system consisted of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220.
  • the column and carousel compartments were operated at 140° C.
  • the columns were three Polymer Laboratories, 10-micron Mixed-B columns
  • the solvent used was 1,2,4 trichlorobenzene.
  • the samples were prepared at a concentration of “0.1 gram of polymer in 50 milliliters of solvent.”
  • the solvent used to prepare the samples contained “200 ppm of butylated hydroxytoluene (BHT).” Samples were prepared by agitating lightly for two hours at 160° C.
  • the injection volume was 100 microliters, and the flow rate was 1.0 milliliters/minute.
  • Calibration of the GPC column set was performed with 21 “narrow molecular weight distribution polystyrene standards,” with molecular weights ranging from 580 to 8,400,000 g/mole, arranged in six “cocktail” mixtures, with at least a decade of separation between individual molecular weights.
  • the standards were purchased from Polymer Laboratories (Shropshire, UK).
  • the polystyrene standards were prepared at “0.025 grams in 50 milliliters of solvent” for molecular weights equal to, or greater than, 1,000 kg/mol, and “0.05 grams in 50 milliliters of solvent” for molecular weights less than 1,000 kg/mol.
  • the polystyrene standards were dissolved at 80 degrees Celsius, with gentle agitation, for 30 minutes.
  • the narrow standards mixtures were run first, and in order of decreasing “highest molecular weight” component to minimize degradation.
  • the terpolymers containing ethylene, propylene, and 5-ethylidene-2-norbornene were analyzed using ASTM D3900 for its ethylene content, and ASTM D6047 for its ethylidene-norbornene or dicyclopentadiene content.
  • the samples were prepared by adding approximately “2.6 g” of a “50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene” that is “0.025M” in chromium acetylacetonate (relaxation agent) to “0.2 g sample” in a 10 mm NMR tube.
  • the samples were dissolved, and homogenized, by heating the tube and its contents to 150° C.
  • the data were collected using a Bruker 400 MHz spectrometer, equipped with a Bruker Dual DUL high-temperature CryoProbe.
  • the data was acquired using “160 scans per data file,” a six second pulse repetition delay, with a sample temperature of 120° C.
  • Specimens for Dynamic Mechanical Spectroscopy were “25 mm diameter ⁇ 3.3 mm thick” compression molded discs, formed at 180° C., and 10 MPa molding pressure, for five minutes, and then quenched between chilled platens (15-20° C.) for two minutes.
  • the rheology ratio (V0.1/V100 at 190° C.; also referred to as “RR”) was recorded.
  • a linear molecule typically has a RR of 8 or less.
  • Compression set was measured according to ASTM D395 at 23° C. and 100° C. Disks of 29 mm ( ⁇ 0.5 mm) in diameter and 12.7 mm ( ⁇ 0.5mm) thickness, were punched from compression molded plaques, prepared as described under the section for compression molding. Each button sample was inspected for notches, uneven thickness and inhomogeneity, and selected buttons (without those defects) were tested. Compression set was performed on two specimens for each sample, at the temperatures specified, and the average results of the two specimens was reported. The button sample was placed in the compression device having two metal plates that could be pressed together, and locked into place at 75% of the original height of the button sample.
  • Tensile properties were measured using specimens which were die cut, using a small “dog bone” shaped micro tensile die, having the dimensions described in ASTM D-1708. The die cut specimens were cut from the compression molded plaques, which were prepared as described under the Compression Molding section. Tensile properties (tensile strength and elongation) were measured at room temperature, following the method ASTM D-412, in the machine direction of an INSTRON MODEL 1122, made by INSTRU-MET.
  • Sample specimens were cut from compression molded plaques, which were prepared as described in the compression molding section.
  • Shore A hardness was measured per ASTM D2240, on a Shore A Durometer Model 2000, made by INSTRON, with a Durometer Stand Model 902. This method permits hardness measurements, based on either initial indentation, or indentation after a specific period of time, or both. As used herein, the indentation was measured at a specified time of ten seconds.
  • the physical properties of the formulations were measured from plaques, cured in a compression molder (for tensile, compression set testing, C-tear, temperature retraction). The samples were compression molded, in accordance to ASTM D3182, using a PHI (100 ton press).
  • the desired mold (6 in. ⁇ 6 in., or compression buttons) was placed on a platen.
  • the sample (uncured blanket) was cut slightly smaller than the dimensions of the individual mold cavity. The mill direction was marked, and the sample was labeled.
  • the mold was spray brushed with a dilute solution of silicone.
  • the samples were in a preheated mold, taking care to place properly for mill direction.
  • the platens were closed.
  • the “normal” operating pressure was 100 tons, or as shown on the gauge as 200,000 pounds.
  • the bottom platen automatically opened.
  • the samples were removed, and immediately placed in water to stop the curing. Samples were conditioned for 24 hours at room temperature, prior to testing. To vulcanize the samples, the samples were conditioned at 160° C. using t95 data plus three minutes for plaques, and using t95 data plus 15 minutes for compression set buttons.
  • Mooney Viscosity (ML1+4 at 125° C.) was measured in accordance with ASTM 1646, with a one minute preheat time and a four minute rotor operation time.
  • the instrument is an Alpha Technologies Mooney Viscometer 2000.
  • Scorch properties of each composition was measured in accordance to ASTM D-1646, using an Alpha Technologies Mooney Viscometer 2000. Mooney viscometer was set at 125° C. The Mooney scorch values were reported for a small rotor, and represented the time to rise “x Mooney units” above the minimum viscosity (e.g. t 5 is a “five Mooney unit” increase in viscosity). The total test time was 30 minutes, with a 1 minute preheat time. The viscosity of the compositions were measured from uncured blanket, cured in the viscometer, so that the scorch properties could be examined Samples were conditioned for 24 hours at room temperature, prior to testing.
  • MDR cure properties of each formulation were measured in accordance to ASTM D-3182, using an Alpha Technologies Rheometer MDR 2000. The MDR Test was carried out at 160° C. over a period of 30 minutes. The rheology of each formulated composition was measured from samples of uncured blanket, which was then cured during the MDR analysis. Samples were conditioned for 24 hours at room temperature, prior to testing. The visco-elastic properties, such as Mooney low, Mooney high, tan delta low, tan delta high, and time to reach a certain percentage of the cure state (for example, t95 corresponds to the time in minutes to reach the 95% state of cure), were measured during the cure cycle.
  • the temperature retraction properties of the cured specimens were measured in accordance to ASTM D-1329. Retraction at Lower Temperatures using MODEL # TR-6 (BENZ Materials). This test method describes a temperature-retraction procedure for rapid evaluation of crystallization effects and for comparing visco-elastic properties of rubber and rubber-like materials at low temperatures.
  • the initial specimen had dimensions of “48 mm by 120 mm by 2 mm,” and was die cut according to the shape described in ASTM D-1329.
  • This test method was carried out by elongating the specimen to 150%, locking specimen in the elongated condition, freezing specimen to a state of reduced elasticity ( ⁇ 45° C.), equilibrating the specimen for ten minutes, releasing the frozen specimen, and allowing specimen to retract freely, while raising the temperature at 1° c./min, measuring the length of the specimen at regular temperature intervals, while it is retracting, and computing the percentage retraction at these temperatures from the data obtained.
  • the temperatures corresponding to 10% and 70% retraction are of particular importance, and are designated as TR10 and TR70, respectively.
  • C-Tear properties were measured using specimens which were die cut, using a die, having the dimensions described in ASTM D-624.
  • the die cut specimens were cut from the cured and compression molded plaques, which were prepared as described under the
  • the specimens were conditioned at ASTM conditions (23+/ ⁇ 2° C. and 50% RH) for at least 16 hours, before they were died out and tested. Tear properties were measured, at room temperature, following the method ASTM D-624, and were measured in the mill direction using an INSTRON MODEL 1122, made by INSTRU-MET. The gauge length between the grips was set to be 50.8 mm, and the testing speed was carried out at 508 mm/min The average C tear strength was reported in N/mm.
  • the polymer products were produced in a solution polymerization process using a series of continuously mixed reactors; loop or continuous stir-tanked reactor configured in a single or dual reactor configuration. See also U.S. Pat. Nos. 5,977,251 and 6,545,088, and the references therein, for reactors and associated equipment and polymerization conditions.
  • Ethylene was introduced in a mixture of a solvent of ISOPAR E (a mixture of C8-C10 saturated hydrocarbons available from ExxonMobil), propylene and 5-ethylidene-2-norbornene (ENB), forming the reactor feed streams.
  • Catalyst was fed individually to each reactor separately, and activated in-situ using co-catalyst 1 and co-catalyst 2.
  • the outlet of each reactor was consequently a mixture of polymer, solvent, and reduced levels of the initial monomer streams; outlet of the first reactor was fed directly into the second reactor (unless otherwise sampled).
  • the molecular weight of the polymer may be controlled by adjusting each reactor's temperature, monomer conversion and/or the addition of a chain terminating agent such as hydrogen.
  • the polymerization reactions were performed under steady state conditions, that is, constant reactant concentration and continual input of solvent, monomers, and catalyst, and withdrawal of unreacted monomers, solvent and polymer.
  • the reactor system was cooled and pressured to prevent formation of a vapor phase.
  • EPDM01 was prepared using two consecutive loop reactors (first reactor: loop;
  • second (final) reactor loop
  • EPDM02 and EPDM03 were each prepared using a loop reactor followed by a continuous stirred-tank reactor (first reactor: loop; second (final) reactor: CSTR).
  • first reactor loop
  • second (final) reactor CSTR
  • Examples designated with “R1” are of the materials sampled from the first reactor and are representative of the polymer composition that is fed to the second reactor.
  • Polymer properties are shown in Tables 2.
  • Comparative resins are shown in Table 3.
  • **Cocatalyst-1 was a mixture of methyldi(C14-18 alkyl)ammonium salts of tetrakis(pentafluorophenyl)borate, prepared by reaction of a long chain trialkylamine (ARMEEN M2HT, available from Akzo-Nobel, Inc.), HCl and Li[B(C6F5)4], substantially as disclosed in U.S. Pat. No. 5,919,988 (Ex. 2).
  • Cocatalyst-1 was purchased from Boulder Scientific, and used without further purification.
  • ***Cocatalyst-2 modified methylalumoxane (MMAO) was purchased from Akzo Nobel, and used without further purification.
  • Each formulation for cure contained sulfur, accelerators, carbon black, zinc oxide, oil, as shown below in Table 4.
  • Each formulation was shear mixed in a BANBURY mixer (starting from room temperature), and then milled into flat blankets using a roll-mill
  • the formulation was mixed using a Farrel BR Banbury Mixer (1.5 L volume) using an upside down mixing method.
  • the polymer was weighed in with the sulfur and other dry ingredients, and fluxed at a slow-speed for 2.5 minutes, at 66° C. (150° F.); the accelerator was added, and then the mixture was further fluxed, and then dropped at 99° C. (210° F.).
  • a 6′′ Reliable Roll Mill was then used to complete the mixing and to mill an uncured blanket. Blowing agents can be added to produce sponge products. Different and additional cross-linking agents, such as peroxides, can be used.
  • Samples from the uncured blankets were heated and cured in a compression molder (see Test Method section), and the properties tested on the cured specimen. Samples from the uncured blankets were heated in a rheometer (see Test Method section), and the curing rates of the samples were examined. Properties are shown in Tables 5 and 6.
  • FIG. 1 depicts a plot of “13C NMR % Peak Area” versus “weight percent C2” for several inventive (first composition) and comparative compositions.
  • the comparative compositions are listed in Table 7, and the inventive compositions are listed in Table 8.
  • the increased tacticity is a result of the catalyst and process, and the specific polymer that is produced.
  • the % mm tacticity increases with decreasing ethylene content in the polymer.
  • the inventive compositions have high levels of % mm tacticity.
  • Increased compatibility with the oils, fillers, curatives, and other polymers allows for improved dispersion of the formulation components, resulting in smoother surfaces of extruded, molded, rolled, or calendared articles, and less imperfections and defects due to undispersed components. Improved dispersion allows for shorter mixing times; shorter mixing times allow for simpler mixing equipment, which can be used to achieve the degree of dispersion necessary for typical applications.
  • compositions containing around 70 wt % of ethylene (C2) the respective inventive composition containing EPDM01 had similar cure properties and physical properties as the composition containing EPDM25.
  • compositions containing around 50 wt % of ethylene (C2) the respective inventive compositions containing EPDM02 and EPDM03 had similar cure properties and physical properties as the composition containing EPDM70.
  • the dispersion and mixing of the polymer also is a function of the rheology of the polymer, as indicated by the low shear viscosity at 0.1 (rad/s) and the rheology ratio (V0.1 (viscosity at 0.1 rad/s)/V100 (viscosity at 100 rad/s)).
  • V0.1 viscosity at 0.1 rad/s
  • V100 viscosity at 100 rad/s
  • high rheology ratios are preferred because they give rise to lower viscosity as the shear conditions in the mixture increase.
  • the EPDM01-R1 (first reactor) polymer had a higher rheology ratio.
  • EPDM25 (first reactor) had a rheology ratio of 38, while EPDM01-R1 (first reactor) had a rheology ratio of 65.5. Also, EPDM25 (final polymer composition) had a rheology ratio of 16.0, while EPDM01 (final polymer composition) had a rheology ratio of 37.7.
  • a lower tan delta, at 0.1 rad/s is preferred, because it gives rise to higher melt elasticity at low shear rates.
  • the high melt elasticity of the polymer can aid in the break-up and dispersion of other components, by acting as a shear promoter that helps maintain a high viscosity, until the stresses are reduced from the melting and dispersion of the polymer.
  • EPDM25 has a tan delta, at 0.1 rad/s, of 2.0, while the tan delta, at 0.1 rad/s, for EPDM01 is 1.27.
  • EPDM01-R1(first reactor) Compared to EPDM25 (first reactor), EPDM01-R1(first reactor) and has a lower tan delta, at 0.1 rad/s.
  • First reactor polymer from EPDM25 had a tan delta, at 0.1 rad/s, of 1.0, while the tan delta, at 0.1 rad/s, for EPDM01-R1 is 0.79.
  • the viscosity and rheological features, along with the “% mm tacticity,” provide a unique viscosity and component compatibility that results in a polymer composition that is easily dispersed in a rubber compound. Such features are important for obtaining fine dispersion of the components added to a rubber formulation, such as carbon black, oils, curatives, talc, calcium carbonate, and other additives. Benefits are expected in the rubber mixing operations and in the processing of final articles, such as extruded profiles, injection molded articles, rolled and calendared articles.

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